Hair Care Compositions Comprising a Dendritic Polymer

ABSTRACT

A cosmetic and personal care composition comprising a hydrophobically functionalised polyhydric dendritic macro-molecule built up from polyester or polyether units or mixtures thereof.

FIELD OF THE INVENTION

The present invention relates to cosmetic and personal carecompositions, in particular the present invention relates to hair carecompositions that leave the hair straight, well aligned and withdecreased volume.

BACKGROUND AND PRIOR ART

Straight, perfectly aligned, long hair is seen by many people asattractive. The present application discloses formulations for aligninghair, preventing hair frizzing and decreasing the volume of hair.

Certain dendritic polymers have been suggested for use in the context ofpersonal care.

WO 01/17485 discloses the use of dendritic molecules to style hair,leave-in formulations are preferred particularly hair stylingcompositions such as hairsprays.

WO97/14404 describes personal wash compositions containing an anionicsurfactant as a cleaning agent and a cationic dendrimer as a mildnessaid. The preferred cationic dendrimers are polyamidoamine (PAMAM)dendrimers prepared by sequential reactions of ethylenediamine andmethyl acrylate.

U.S. Pat. No. 5,449,519 relates to keratolytic or anti-acne compositionsin which the keratolytic or anti-acne agent (e.g. salicylic acid) iscomplexed with a starburst dendrimer of the PAMAM type.

EP 0 880 961 and EP 880 962 describe anti-solar preparations forprotection of skin and hair containing a hyperbranched or dendrimericpolyamino-polymer such as hyperbranched polyethyleneimine.

EP0 884 047 relates to the use of polyamine polymers, which may behyperbranched or dendrimeric, as antioxidant agents for cosmetic ordermatological compositions.

WO 99/32076 and WO 99/32540 concern the use of certain specificdisulphide-functionalised hyperbranched polymers and dendrimers incosmetics and pharmaceuticals as thickening or gelling agents or asfilm-forming agents.

EP 0 815 827 describes cosmetic compositions for treating the hair witha content of at least one dendrimer or dendrimer conjugate in a cosmeticbase. These dendrimers are referred to as poly(iminopropane-1,3-diyl)dendrimers with nitrile or amino terminal groups and their preparationis describes in U.S. Pat. No. 5,530,092.

SUMMARY OF THE INVENTION

The present invention provides a cosmetic and personal care compositioncomprising a hydrophobically functionalised polyhydric dendriticmacromolecule built up from polyester units or polyester or polyetherunits or mixtures thereof

The invention also relates to a method of treating hair by applying theabove composition.

The invention also relates to the use of the dendritic macromoleculedescribed above for aligning the hair. and decreasing the volume ofhair.

DETAILED DESCRIPTION

As used herein, “water-soluble” refers to any material that issufficiently soluble in water to form a clear or translucent solution tothe naked eye at a concentration of 1.0% or more by weight of thematerial in water at 25° C.

Dendritic Macromolecule

Dendritic macromolecules are macromolecules with densely branchedstructures having a large number of end groups. A dendritic polymerincludes several layers or generations of repeating units which allcontain one or more branch points. Dendritic polymers, includingdendrimers and hyperbranched polymers, are prepared by condensationreactions of monomeric units having at least two different types ofreactive groups. Dendrimers are highly symmetric, whereas macromoleculesdesignated as hyperbranched may to a certain degree hold an asymmetry,yet maintaining the highly branched treelike structure.

Dendritic macromolecules normally consist of an initiator or nucleushaving one or more reactive sites and a number of branching layers andoptionally a layer of chain terminating molecules. Continued replicationof branching layers normally yields increased branch multiplicity and,where applicable or desired, increased number of terminal groups. Thelayers are usually called generations and the branches dendrons.

Compositions of the invention comprise a hydrophobically functionaliseddendritic macromolecule. Preferred hydrophobic groups are carbon based.C₂-C₂₄ alkyl or alkenyl groups are preferred hydrophobic groups, morepreferred are C₄-C₂₂ alkyl or alkenyl groups, especially preferred areC₆-C₂₀ alkyl or alkenyl groups, most preferred are dendriticmacromolecule having C₈-C₁₈ alkyl or alkenyl groups. The hydrophobicgroups may include linear and branched hydrophobes as well as arylalkylgroups, however it is preferred if the alkyl hydrophobic groups arelinear. The hydrophobic groups may be unsaturated groups but arepreferably saturated. The hydrophobic groups are sometimes linked to thedendritic macromolecule through linking groups, suitable linking groupsinclude ester or amide groups.

The dendritic macromolecules are built up from polyester or polyetherunits or mixtures thereof. Polyesters are preferred, polyesters areparticularly for shampoos. Polyethers are in some instances preferredfor conditioners. Suitable macromolecules of this type and their methodof manufacture are disclosed in U.S. Pat. No. 5,418,301 and can be soldunder the tradename Perstorp.

It is preferred if the dendritic macromolecule is fully or partiallyhydrophobically functionalised at the periphery and/or the terminalgroups of the dendritic macromolecule. (In the context of the presentinvention the term periphery means the outer layer or edge of thedendritic macromolecule.)

If the dendritic macromolecule is hydrophobically functionalised at theperiphery preferably 5 to 95% of the terminal groups are hydrophobicallyfunctionalised, more preferably from 20 to 90%, most preferably from 25to 80%.

It is preferred if the generation number of the polymer is grater than1, more preferably 2 or greater. The maximum generation number is 10 orless, more preferably 8 or less. A preferred range for the generationnumber is from 2 to 6.

The level of hydrophobically functionalised dendritic macromolecule ispreferably from 0.0001 to 10 wt % of the total composition, morepreferably the level is from 0.001 to 5 wt %, most preferably from 0.01to 3 wt %.

A preferred form of adding the dendritic macromolecule to thecomposition is to add the macromolecule together with any surfactantand/or long chain alcohol.

Product Form

Compositions of the invention are typically “rinse-off” compositions tobe applied to the hair and then rinsed away.

Shampoo Composition

Shampoo compositions of the invention are generally aqueous, i.e. theyhave water or an aqueous solution or a lyotropic liquid crystallinephase as their major component. Suitably, the composition will comprisefrom 50 to 98%, preferably from 60 to 90% water by weight based on thetotal weight of the composition.

Anionic Cleansing Surfactant

Shampoo compositions according to the invention will generally compriseone or more anionic cleansing surfactants which are cosmeticallyacceptable and suitable for topical application to the hair.

Examples of suitable anionic cleansing surfactants are the alkylsulphates, alkyl ether sulphates, alkaryl sulphonates, alkanoylisethionates, alkyl succinates, alkyl sulphosuccinates, alkyl ethersulphosuccinates, N-alkyl sarcosinates, alkyl phosphates, alkyl etherphosphates, and alkyl ether carboxylic acids and salts thereof,especially their sodium, magnesium, ammonium and mono-, di- andtriethanolamine salts. The alkyl and acyl groups generally contain from8 to 18, preferably from 10 to 16 carbon atoms and may be unsaturated.The alkyl ether sulphates, alkyl ether sulphosuccinates, alkyl etherphosphates and alkyl ether carboxylic acids and salts thereof maycontain from 1 to 20 ethylene oxide or propylene oxide units permolecule.

Typical anionic cleansing surfactants for use in shampoo compositions ofthe invention include sodium oleyl succinate, ammonium laurylsulphosuccinate, sodium lauryl sulphate, sodium lauryl ether sulphate,sodium lauryl ether sulphosuccinate, ammonium lauryl sulphate, ammoniumlauryl ether sulphate, sodium dodecylbenzene sulphonate, triethanolaminedodecylbenzene sulphonate, sodium cocoyl isethionate, sodium laurylisethionate, lauryl ether carboxylic acid and sodium N-laurylsarcosinate.

Preferred anionic cleansing surfactants are sodium lauryl sulphate,sodium lauryl ether sulphate(n)EO, (where n is from 1 to 3), sodiumlauryl ether sulphosuccinate(n)EO, (where n is from 1 to 3), ammoniumlauryl sulphate, ammonium lauryl ether sulphate(n)EO, (where n is from 1to 3), sodium cocoyl isethionate and lauryl ether carboxylic acid (n) EO(where n is from 10 to 20).

Mixtures of any of the foregoing anionic cleansing surfactants may alsobe suitable.

The total amount of anionic cleansing surfactant in shampoo compositionsof the invention generally ranges from 0.5 to 45%, preferably from 1.5to 35%, more preferably from 5 to 20% by total weight anionic cleansingsurfactant based on the total weight of the composition.

Further Ingredients

Optionally, a shampoo composition of the invention may contain furtheringredients as described below to enhance performance and/or consumeracceptability.

Co-surfactant

The composition can include co-surfactants, to help impart aesthetic,physical or cleansing properties to the composition.

An example of a co-surfactant is a nonionic surfactant, which can beincluded in an amount ranging from 0.5 to 8%, preferably from 2 to 5% byweight based on the total weight of the composition.

For example, representative nonionic surfactants that can be included inshampoo compositions of the invention include condensation products ofaliphatic (C₈-C₁₈) primary or secondary linear or branched chainalcohols or phenols with alkylene oxides, usually ethylene oxide andgenerally having from 6 to 30 ethylene oxide groups.

Other representative nonionic surfactants include mono- or di-alkylalkanolamides. Examples include coco mono- or di-ethanolamide and cocomono-isopropanolamide.

Further nonionic surfactants which can be included in shampoocompositions of the invention are the alkyl polyglycosides (APGs).Typically, the APG is one which comprises an alkyl group connected(optionally via a bridging group) to a block of one or more glycosylgroups. Preferred APGs are defined by the following formula:

RO-(G)_(n)

wherein R is a branched or straight chain alkyl group which may besaturated or unsaturated and G is a saccharide group. n, may have avalue of from about 1 to about 10 or more. materials identified as:Oramix NS10 ex Seppic; Plantaren 1200 and Plantaren 2000 ex Henkel.

A preferred example of a co-surfactant is an amphoteric or zwitterionicsurfactant, which can be included in an amount ranging from 0.5 to about8%, preferably from 1 to 4% by weight based on the total weight of thecomposition.

Examples of amphoteric or zwitterionic surfactants include alkyl amineoxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulphobetaines(sultaines), alkyl glycinates, alkyl carboxyglycinates, alkylamphoacetates, alkyl amphopropionates, alkylamphoglycinates, alkylamidopropyl hydroxysultaines, acyl taurates and acyl glutamates, whereinthe alkyl and acyl groups have from 8 to 19 carbon atoms. Typicalamphoteric and zwitterionic surfactants for use in shampoos of theinvention include lauryl amine oxide, cocodimethyl sulphopropyl betaine,lauryl betaine, cocamidopropyl betaine and sodium cocoamphoacetate.

A particularly preferred amphoteric or zwitterionic surfactant iscocamidopropyl betaine.

Mixtures of any of the foregoing amphoteric or zwitterionic surfactantsmay also be suitable. Preferred mixtures are those of cocamidopropylbetaine with further amphoteric or zwitterionic surfactants as describedabove. A preferred further amphoteric or zwitterionic surfactant issodium cocoamphoacetate.

The total amount of surfactant (including any co-surfactant, and/or anyemulsifier) in a shampoo composition of the invention is generally from1 to 50%, preferably from 2 to 40%, more preferably from 10 to 25% bytotal weight surfactant based on the total weight of the composition.

Cationic Polymers

Cationic polymers are preferred ingredients in a shampoo composition ofthe invention for enhancing conditioning performance.

Suitable cationic polymers may be homopolymers, which are cationicallysubstituted or may be formed from two or more types of monomers. Theweight average (M_(w)) molecular weight of the polymers will generallybe between 100 000 and 2 million daltons.

Suitable cationic polymers include, for example, copolymers of vinylmonomers having cationic amine or quaternary ammonium functionalitieswith water soluble spacer monomers such as (meth)acrylamide, alkyl anddialkyl (meth)acrylamides, alkyl (meth)acrylate, vinyl caprolactone andvinyl pyrrolidine. The alkyl and dialkyl substituted monomers preferablyhave C1-C7 alkyl groups, more preferably C1-3 alkyl groups. Othersuitable spacers include vinyl esters, vinyl alcohol, maleic anhydride,propylene glycol and ethylene glycol.

Cationic amines can be primary, secondary or tertiary amines, dependingupon the particular species and the pH of the composition. In generalsecondary and tertiary amines, especially tertiary, are preferred.

Amine substituted vinyl monomers and amines can be polymerised in theamine form and then converted to ammonium by quaternization.

The cationic polymers can comprise mixtures of monomer units derivedfrom amine- and/or quaternary ammonium-substituted monomer and/orcompatible spacer monomers.

Suitable cationic polymers include, for example:

-   -   cationic diallyl quaternary ammonium-containing polymers        including, for example, dimethyldiallylammonium chloride        homopolymer and copolymers of acrylamide and        dimethyldiallylammonium chloride, referred to in the industry        (CTFA) as Polyquaternium 6 and Polyquaternium 7, respectively;    -   mineral acid salts of amino-alkyl esters of homo- and        co-polymers of unsaturated carboxylic acids having from 3 to 5        carbon atoms, (as described in U.S. Pat. No. 4,009,256);    -   cationic polyacrylamides(as described in WO95/22311).

Other cationic polymers that can be used include cationic polysaccharidepolymers, such as cationic cellulose derivatives, cationic starchderivatives, and cationic guar gum derivatives.

Cationic polysaccharide polymers suitable for use in compositions of theinvention include monomers of the formula:

A-O—[R—N⁺(R¹)(R²)(R³)X⁻],

wherein: A is an anhydroglucose residual group, such as a starch orcellulose anhydroglucose residual. R is an alkylene, oxyalkylene,polyoxyalkylene, or hydroxyalkylene group, or combination thereof. R¹,R² and R³ independently represent alkyl, aryl, alkylaryl, arylalkyl,alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18carbon atoms. The total number of carbon atoms for each cationic moiety(i.e., the sum of carbon atoms in R¹, R² and R³) is preferably about 20or less, and X is an anionic counterion.

Another type of cationic cellulose includes the polymeric quaternaryammonium salts of hydroxyethyl cellulose reacted with lauryl dimethylammonium-substituted epoxide, referred to in the industry (CTFA) asPolyquaternium 24. These materials are available from the AmercholCorporation, for instance under the tradename Polymer LM-200.

Other suitable cationic polysaccharide polymers include quaternarynitrogen-containing cellulose ethers (e.g. as described in U.S. Pat. No.3,962,418), and copolymers of etherified cellulose and starch (e.g. asdescribed in U.S. Pat. No. 3,958,581).

A particularly suitable type of cationic polysaccharide polymer that canbe used is a cationic guar gum derivative, such as guarhydroxypropyltrimethylammonium chloride (commercially available fromRhodia in their JAGUAR trademark series). Examples of such materials areJAGUAR C13S, JAGUAR C14, JAGUAR C15, JAGUAR C17 and JAGUAR C16 JaguarCHT and JAGUAR C162.

Mixtures of any of the above cationic polymers may be used.

Cationic polymer will generally be present in a shampoo composition ofthe invention at levels of from 0.01 to 5%, preferably from 0.05 to 1%,more preferably from 0.08 to 0.5% by total weight of cationic polymerbased on the total weight of the composition.

Suspending Agent

Preferably an aqueous shampoo composition of the invention furthercomprises a suspending agent. Suitable suspending agents are selectedfrom polyacrylic acids, cross-linked polymers of acrylic acid,copolymers of acrylic acid with a hydrophobic monomer, copolymers ofcarboxylic acid-containing monomers and acrylic esters, cross-linkedcopolymers of acrylic acid and acrylate esters, heteropolysaccharidegums and crystalline long chain acyl derivatives. The long chain acylderivative is desirably selected from ethylene glycol stearate,alkanolamides of fatty acids having from 16 to 22 carbon atoms andmixtures thereof. Ethylene glycol distearate and polyethylene glycol 3distearate are preferred long chain acyl derivatives, since these impartpearlescence to the composition. Polyacrylic acid is availablecommercially as Carbopol 420, Carbopol 488 or Carbopol 493. Polymers ofacrylic acid cross-linked with a polyfunctional agent may also be used;they are available commercially as Carbopol 910, Carbopol 934, Carbopol941 and Carbopol 980. An example of a suitable copolymer of a carboxylicacid containing monomer and acrylic acid esters is Carbopol 1342. AllCarbopol (trademark) materials are available from Goodrich.

Suitable cross-linked polymers of acrylic acid and acrylate esters arePemulen TR1 or Pemulen TR2. A suitable heteropolysaccharide gum isxanthan gum, for example that available as Kelzan mu.

Mixtures of any of the above suspending agents may be used. Preferred isa mixture of cross-linked polymer of acrylic acid and crystalline longchain acyl derivative.

Suspending agent will generally be present in a shampoo composition ofthe invention at levels of from 0.1 to 10%, preferably from 0.5 to 6%,more preferably from 0.9 to 4% by total weight of suspending agent basedon the total weight of the composition.

Conditioner Compositions

Another preferred product form for compositions in accordance with theinvention is a conditioner for the treatment of hair (typically aftershampooing) and subsequent rinsing.

Such conditioner compositions will typically comprise one or moreconditioning surfactants, which are cosmetically acceptable and suitablefor topical application to the hair.

Suitable conditioning surfactants include those selected from cationicsurfactants, used singly or in admixture. Preferably, the cationicsurfactants have the formula N⁺R¹R²R³R⁴ wherein R¹, R², R³ and R⁴ areindependently (C₁ to C₃₀) alkyl or benzyl. Preferably, one, two or threeof R¹, R², R³ and R⁴ are independently (C₄ to C₃₀) alkyl and the otherR¹, R², R³ and R⁴ group or groups are (C₁-C₆) alkyl or benzyl. Morepreferably, one or two of R¹, R², R³ and R⁴ are independently (C₆ toC₃₀) alkyl and the other R¹, R², R³ and R⁴ groups are (C₁-C₆) alkyl orbenzyl groups. Optionally, the alkyl groups may comprise one or moreester (—OCO— or —COO—) and/or ether (—O—) linkages within the alkylchain. Alkyl groups may optionally be substituted with one or morehydroxyl groups. Alkyl groups may be straight chain or branched and, foralkyl groups having 3 or more carbon atoms, cyclic. The alkyl groups maybe saturated or may contain one or more carbon-carbon double bonds (eg,oleyl). Alkyl groups are optionally ethoxylated on the alkyl chain withone or more ethyleneoxy groups.

Suitable cationic surfactants for use in conditioner compositionsaccording to the invention include cetyltrimethylammonium chloride,behenyltrimethylammonium chloride, cetylpyridinium chloride,tetramethylammonium chloride, tetraethylammonium chloride,octyltrimethylammonium chloride, dodecyltrimethylammonium chloride,hexadecyltrimethylammonium chloride, octyldimethylbenzylammoniumchloride, decyldimethylbenzylammonium chloride,stearyldimethylbenzylammonium chloride, didodecyldimethylammoniumchloride, dioctadecyldimethylammonium chloride, tallowtrimethylammoniumchloride, dihydrogenated tallow dimethyl ammonium chloride (eg, Arquad2HT/75 from Akzo Nobel), cocotrimethylammonium chloride,PEG-2-oleammonium chloride and the corresponding hydroxides thereof.Further suitable cationic surfactants include those materials having theCTFA designations Quaternium-5, Quaternium-31 and Quaternium-18.Mixtures of any of the foregoing materials may also be suitable. Aparticularly useful cationic surfactant for use in conditionersaccording to the invention is cetyltrimethylammonium chloride, availablecommercially, for example as GENAMIN CTAC, ex Hoechst Celanese. Anotherparticularly useful cationic surfactant for use in conditionersaccording to the invention is behenyltrimethylammonium chloride,available commercially, for example as GENAMIN KDMP, ex Clariant.

Another example of a class of suitable cationic surfactants for use inthe invention, either alone or together with one or more other cationicsurfactants, is a combination of an amidoamine and an acid.

Preferred amidoamines useful herein includestearamidopropyldimethylamine, stearamidopropyldiethylamine,stearamidoethyldiethylamine, stearamidoethyldimethylamine,palmitamidopropyldimethylamine, palmitamidopropyldiethylamine,palmitamidoethyldiethylamine, palmitamidoethyldimethylamine,behenamidopropyldimethylamine, behenamidopropyldiethylmine,behenamidoethyldiethylamine, behenamidoethyldimethylamine,arachidamidopropyldimethylamine, arachidamidopropyldiethylamine,arachidamidoethyldiethylamine, arachidamidoethyldimethylamine, andmixtures thereof.

Particularly preferred amidoamines useful herein arestearamidopropyldimethylamine, stearamidoethyldiethylamine, and mixturesthereof.

Acid (ii) may be any organic or mineral acid which is capable ofprotonating the amidoamine in the hair treatment composition. Suitableacids useful herein include hydrochloric acid, acetic acid, tartaricacid, fumaric acid, lactic acid, malic acid, succinic acid, and mixturesthereof. Preferably, the acid is selected from the group consisting ofacetic acid, tartaric acid, hydrochloric acid, fumaric acid, andmixtures thereof.

Suitably, the acid is included in a sufficient amount to protonate allthe amidoamine present, i.e. at a level which is at least equimolar tothe amount of amidoamine present in the composition.

In conditioners of the invention, the level of cationic surfactant willgenerally range from 0.01 to 10%, more preferably 0.05 to 7.5%, mostpreferably 0.1 to 5% by weight of the composition.

Conditioners of the invention will typically also incorporate a fattyalcohol. The combined use of fatty alcohols and cationic surfactants inconditioning compositions is believed to be especially advantageous,because this leads to the formation of a lamellar phase, in which thecationic surfactant is dispersed.

Representative fatty alcohols comprise from 8 to 22 carbon atoms, morepreferably 16 to 22. Fatty alcohols are typically compounds containingstraight chain alkyl groups. Examples of suitable fatty alcohols includecetyl alcohol, stearyl alcohol and mixtures thereof. The use of thesematerials is also advantageous in that they contribute to the overallconditioning properties of compositions of the invention.

The level of fatty alcohol in conditioners of the invention willgenerally range from 0.01 to 10%, preferably from 0.1 to 8%, morepreferably from 0.2 to 7%, most preferably from 0.3 to 6% by weight ofthe composition. The weight ratio of cationic surfactant to fattyalcohol is suitably from 1:1 to 1:10, preferably from 1:1.5 to 1:8,optimally from 1:2 to 1:5. If the weight ratio of cationic surfactant tofatty alcohol is too high, this can lead to eye irritancy from thecomposition. If it is too low, it can make the hair feel squeaky forsome consumers.

Further Conditioning Agents

Compositions of the invention may comprise further conditioning agentsto optimise wet and dry conditioning benefits.

Particularly preferred further conditioning agents are siliconeemulsions.

Suitable silicone emulsions include those formed from silicones such aspolydiorganosiloxanes, in particular polydimethylsiloxanes which havethe CTFA designation dimethicone, polydimethyl siloxanes having hydroxylend groups which have the CTFA designation dimethiconol, andamino-functional polydimethyl siloxanes which have the CTFA designationamodimethicone.

The emulsion droplets may typically have a Sauter mean droplet diameter(D_(3,2)) in the composition of the invention ranging from 0.01 to 20micrometer, more preferably from 0.2 to 10 micrometer.

A suitable method for measuring the Sauter mean droplet diameter(D_(3,2)) is by laser light scattering using an instrument such as aMalvern Mastersizer.

Suitable silicone emulsions for use in compositions of the invention areavailable from suppliers of silicones such as Dow Corning and GESilicones. The use of such pre-formed silicone emulsions is preferredfor ease of processing and control of silicone particle size. Suchpre-formed silicone emulsions will typically additionally comprise asuitable emulsifier such as an anionic or nonionic emulsifier, ormixture thereof, and may be prepared by a chemical emulsificationprocess such as emulsion polymerisation, or by mechanical emulsificationusing a high shear mixer. Pre-formed silicone emulsions having a Sautermean droplet diameter (D_(3,2)) of less than 0.15 micrometers aregenerally termed microemulsions.

Examples of suitable pre-formed silicone emulsions include emulsionsDC2-1766, DC2-1784, DC-1785, DC-1786, DC-1788 and microemulsionsDC2-1865 and DC2-1870, all available from Dow Corning. These are allemulsions/microemulsions of dimethiconol. Also suitable areamodimethicone emulsions such as DC939 (from Dow Corning) and SME253(from GE Silicones).

Also suitable are silicone emulsions in which certain types of surfaceactive block copolymers of a high molecular weight have been blendedwith the silicone emulsion droplets, as described for example inWO03/094874. In such materials, the silicone emulsion droplets arepreferably formed from polydiorganosiloxanes such as those describedabove. One preferred form of the surface active block copolymer isaccording to the following formula:

wherein the mean value of x is 4 or more and the mean value of y is 25or more.

Another preferred form of the surface active block copolymer isaccording to the following formula:

wherein the mean value of a is 2 or more and the mean value of b is 6 ormore.

Mixtures of any of the above described silicone emulsions may also beused.

Silicone will generally be present in a composition of the invention atlevels of from 0.05 to 10%, preferably 0.05 to 5%, more preferably from0.5 to 2% by total weight of silicone based on the total weight of thecomposition.

Other Optional Ingredients

A composition of the invention may contain other ingredients forenhancing performance and/or consumer acceptability.

Such ingredients include fragrance, dyes and pigments, pH adjustingagents, pearlescers or opacifiers, viscosity modifiers, preservatives,and natural hair nutrients such as botanicals, fruit extracts, sugarderivatives and amino acids.

The invention is further illustrated with reference to the following,non-limiting examples, in which all percentages are by weight based ontotal weight unless otherwise specified.

Examples of the invention are illustrated by a number, comparativeexamples are illustrated by a letter.

EXAMPLES Shampoo

Various shampoo compositions were prepared using as a basis theformulation in table 1.

TABLE 1 Weight Chemical name (as 100% active) Sodium laureth (2 EO)sulphate 14.0 (SLES) Coco amidopropyl betaine (CAPB) 2.0 Guarhydroxypropyl 0.4 trimonium chloride Silicone emulsion 2.0 dendriticpolymer (See table 3) 2.0 sodium chloride q.s. water and minors To 100%

Shampoo examples were made up using the relevant Boltorn as detailed intable 2. Shampoo example A was made up without Boltorn present.

Conditioner

Various conditioner compositions were prepared using as a basis theformulation in table 2.

TABLE 2 Weight (as 100% Chemical name active) Cetyl Trimethyl AmmoniumChloride 0.9 Dioctadecyl Dimethyl Ammonium Chloride 0.4 Cetearyl alcohol4.0 Silicone emulsion 2.0 dendritic polymer (table 4) 2.0 Water andminors To 100%

Conditioner examples were made up using the relevant Boltorn at 2%unless otherwise indicated as detailed in table 4. Conditioner example Bwas made up without Boltorn present.

In-vitro Test Method

Laser Volume Experiment (Switches Treated with Shampoo and/orConditioner)

Base Wash

2 g/10″ European hair switches were base washed using a 14/2 SLES/CAPBsolution. 5 switches were grouped together and wetted under runningwater at 35-40° C. The excess water was removed by running thumb andforefinger along the length of the switch. 1 ml of base was appliedalong the length of the switch and agitated for 30 seconds. The switchwas rinsed under the warm running water for 30 seconds and then afurther 1 ml of SLES/CAPB was applied and agitated for another 30seconds. The switch was given a final rinse for 1 minute.

Shampoo Treatment

5 switches were grouped together and 1 ml of shampoo was placed alongthe length of the switch. The switch was agitated for 30 seconds,followed by a rinse for 30 seconds. Another 1 ml of shampoo was placedalong the length of the switch and agitated for 30 seconds, followed bya rinse for 1 minute. The switches were combed through whilst suspendedvertically from a clamp stand, the switch was smoothed by running thumband forefinger along the length of the switch and then allowed to drynaturally overnight. Note 5 switches were used per treatment.

Conditioner Treatment

5 switches were grouped together and base washed as above with 14/2shampoo, then 2 mls of conditioner was placed along the length of theswitch and agitated for 1 minute followed by a rinse for 1 minute. Theswitches were combed through whilst suspended vertically from a clampstand, the switch was smoothed by running thumb and forefinger along thelength of the switch and then allowed to dry naturally overnight.

Laser Measurements

Each switch was suspended vertically from a clamp stand and a 2 mW, λ(wavelength)=632.8 nm Helium-Neon laser shone perpendicular to theuntouched switch approximately 2″ from the bottom of the switch. Thelaser illuminated a cross-section of the switch creating a twodimensional image of white dots on a dark background with each dotrepresenting a single hair fibre. The illuminated image was recordedonto an optical disc using a 35 mm camera.

Analysis

A macro was used to set the discrimination level for each image, (i.e.the threshold value for a clear image resulting in the no. of dotsstored onto the disc) and then calculate the x,y co-ordinates of everydot on the image. Another macro in Excel applied a mathematicaltransformation on all the co-ordinates, to convert the co-ordinates fromtheir apparent position relative to the camera to their actual positionin the switch. These actual co-ordinates were used to calculate the meanradial distribution of all the co-ordinates away from the calculatedcentre, thus providing an indicator for the volume of the switch.

Analysis Results

The volume was normalised with respect to Examples A and B in tables 3and 4 respectively.

Shampoo

TABLE 3 % Alkyl Generation (C₈₋₁₀) Normalised Example Boltorn nameNumber substitution Volume

1 H60 0.8C8-10 6 80 0.71 2 H2004 2 60 0.79 3 H40 0.5C8-10 4 50 0.81 4H40 90% C8/C10 4 90 0.94 5 H2003 2 30 0.98 C H20 2 0 1.02 D H30 3 0 1.01E H40 4 0 1.0 A — 1.00

The lower the number, the lower the volume

Conditioner

TABLE 4 % Alkyl Generation (C₈₋₁₀) Normalised Example Boltorn nameNumber substitution volume  6 H2003 2 30 0.81  7 H40 90% C8/C10 4 900.90  8* W1000 0.93  9 H60 0.8C8-10 6 80 0.94 10 H40 0.5C8-10 6 50 0.9511 1% 2004H 2 60 0.95 F H40 4 0 1.02 G H30 3 0 1.09 H H20 2 0 1.10 B —1.00 *Example 8 is a polyether based dendrimer, end-capped with C18

In-vivo Test Data Salon Workshop

The shampoo formulations were prepared using the formulations in Table5.

TABLE 5 Example C Example 17 Weight Weight (as 100% Chemical name (as100% active) active) Sodium laureth (2 14.0 14.0 EO) sulphate (SLES)Coco amidopropyl 2.0 2.0 betaine Guar hydroxypropyl 0.4 0.4 trimoniumchloride Silicone emulsion 2.0 2.0 Dendritic polymer - 2.0 — H2004Sodium chloride q.s. q.s. Water and minors To 100% To 100%

The dendritic polymer is H2004, see table 3.

Salon Workshop Methodology

2 hairdressers assessed the product (9 panelists for each hairdresser).The shampoo product is applied by applicator as blind test andhairdresser washes panelists accordingly. Each hairdresser assesses andscores the performance of product (pair comparison) and difference scalebetween 2 products.

TABLE 6 Number of Number of times Significance times example C of winover Attribute chosen chosen control Good alignment 13 5 >90% Lessfluffy 13 5 >90% Weighty hair 13 5 >90% Hair volume 13 5 >90% Overallassessment by hairdressers (n = 18)

1. A method of treating hair comprising the step of applying to the haira composition comprising a hydrophobically functionalized polyhydricdendritic macromolecule built up from polyester or polyether units ormixtures thereof.
 2. A method according to claim 1 in which thehydrophobically functionalized group of the dendritic macromoleculecomprises a C₆-C₂₀ carboxyl group.
 3. A method according to claim 1 inwhich the hydrophobically functionalized group of the dendriticmacromolecule comprises a C₈-C₁₈ carboxyl group.
 4. A method accordingto claim 1 in which the hydrophobically functionalized groups of thedendritic macromolecule are situated at the terminals of themacromolecule.
 5. A method according to claim 1 in which the degree ofsubstitution of the alkyl groups is from 20 to 90% of the terminalgroups of the dendritic polymer
 6. A method according to claim 1 inwhich the generation number of the dendritic macromolecule is from 2 to6.
 7. A method to claim 1 in which the level of hydrophobicallyfunctionalized dendritic macromolecule if from 0.001 to 5 wt % of thetotal composition.
 8. A method to claim 1 in which the composition is arinse off composition.
 9. A method to claim 1 which further comprises asilicone conditioning oil.
 10. A method according to claim 1 whichfurther comprises a surfactant.
 11. Use of a hydrophobicallyfunctionalized dendritic macromolecule described above for aligning thehair.
 12. Use of a hydrophobically functionalized dendriticmacromolecule described above for decreasing the volume of hair.